Desulphurizing hydrocarbon oils



R. C. MORAN DESULPHURIZING HYDRocARBoN oILs Nov. 20, 1928. 1,692,756

Filed Jan. 18, 1927 BY www M ATTORNEY v Patented Nov. 20, 41928.

UNITED STATESv .PATENT OFFICE.

ROBERT C. MORAN, 'OF WOODBURY, NEW JERSEY', AssIGN'oR rro VACUUM PANY, oF NEW YORK, N. Y., A CORPORATION OF NEW YORK. i

OIL COM'- DESULIHURIZING IIYDRCAPLBON oII-is.

Abpucation inea January 1a, 1927. serial No 161,784;

The invention relates to processes for the removal or reduction of the sulphur contents of hydro-carbon oils, particularly petroleum, shale oil andother mineral oils, and more 5 particularly vtheir products.

The invention will be described more particularly ivith regard to the treatment of petroleum, and particularly its distillates or products, as motor fuel and lamp oil, Which l for brevity, Will be termed light distillates. Lightdistillates of the character referred to usually contain sulphur, 'eithcrin the free or in,the combined state,or in both states. l The free or elementary sulphur, as Well as numerous fori/nsv of thecombined sulphur, have a corrosive effect on copper, determinableby the Well-known copperdish test (Technical Paper,` Bureau of Mines, No. 323A,pa`ge 86, United States Got/ernment Specifications for Lubricants and Lubricants and Liquid Fuels and Methods for Testing), in accordance with which the oil is evaporated to dryness in a polished copper dish and the presence of black vcorrosion noted. Free or elementary sulphur and those compoundsl of sulphur which soeffect corrosion are for brevity herein andin the ap ended claims termed corrosive sulphur. ertain forms Vof they combined sulphur react to the Well-known fdoctor test ,(afore` said technical paper, page 85),) Whic'h consists in shaking the oijl With a Water solution of sodium plumbitewand powdered sulphur. These compoundsgive a discoloration of the sulphur and/or oil, and the oil containing them is known as sour. These compounds are for brevity herein termed soursulphur v Sulphur beyond certain limits and in certain ,forms objectionable in light disti'llates intended for motor fuel orlamp oil, because ofodor, instability or corrosive action. According tothe United States Government specification (aforesaid technical paper), motor fuel and Alamp oi l must net havea sulphuif content beyond vcertain specified linritsiand,furthermore, must be sweet or ree from sourv sulphur; further specification in the case of motor fuelis `that it must containnojcorrosive sulphur. rllhe most generally used reagent foijpurifiring, and. ,de-,Suil'phurzins lightdistillate i s s1'1lp` l n 1ric acid.1 YVhen light distillates are refined by treating with sulphuric acid,

Which treatment may or may not have been preceded by atreatment for the removalof sour sulphur and followed by Washing with Water and/orhydroxide solution, the purified distillates arenot always free from' corrosive sulphur. The so-purified distillates alivayscontain corrosive sulphur if free or elementary sulphur be present inthe original distillates, or if freeor elementary sulphur b e formedthrough' chemical interaction duringy the refining operation, or if an excess of free or elementary sulphur be used inthe processv of removing sour sulphur fromthe original distillates. i

Light distillates, desulphuried ,by the use of sulphur-ic acid, Which areQstill. corrosive are customarily subjected to a redistillation operation in order to obtair'i non-corrosive products. This ive-distillation operation is, economically, decidedly disadvantageous, involving as it does, practically unavoidable handlingv losses, vdistillation losses, etc. Furthermore, vthe ,re-distilled product may be sour. as a result of the development of sour sulphur during the re-distillation operation. In this event, the redistilled product must be further purified to remove the sour sulphur. Processes, i'vh'ichido not involve redistilla.` tion, have been proposed Vfor the removal of corrosive sulphur from blightl distillatcs Which may rormay not Vhave been previously re'iined'to remove all or a portion ofthe sour sulphur content.Y Such processesnsuaflly involve the use of heat Ora blending operai@l t'ion. Against these processes, vvhichiinvolve the use of heatto produce thedesired effects, may be cited the disadvantagel Yof practically unavoidable .handling and treating losses, While against blending processes may be cite/d the disadvantageofthe rigidity of control ation.

Ithas long been known ythat corrosive sulphur can be removed from1 petroleum by subjecting such oil or its vapor of distillation to contact with molten metals (lead, tin, Zinc, mercury, antinieny) o r ruetafls in a nely-divided condition (iron, copper,v antin1.0ny).@. J, 1. In,th practical adaptation @f .metalsgfor desulphurizing purpose, difliculty met With is thatthe surface ofthe metal sosoon becomes coated With sulphidejasg tomender it inactive, or practically so, for ypurpose of required to ensure their successful operacteristics of mercury as a desulphurizing purification, and unless some means be employed for cleansing the metal so as to present fresh metallic surfaces to the s ulphurinthe oil, this method of purification cannot be economically practiced. v

Of the metals mentioned above as desulphurizing agents, mercury has specially attractive characteristics. It is the most rcactive towards corrosive sulphur; in fact, its reactivity is of such an order that it can produce a desulphurizing effect on an oil under substantially atmospheric temperature conditions which can be equalled or approached by the other metals,ymentioned above'only when heat is applied as anecessary adjunct, Furtliermore,mercury is the only one ofv the above mentioned metals, by treat-ment with which at substantially atmospheric temperatures a corrosive oil can be rendered at once sweet or free of sourv sulphur as well as noncorrosive or free of corrosive sulphur. f

Another specially attractive characteristic of mercury is itsmolten condition at ordinary temperatures which tends to simplication in treating technique. Furthermore, the by-product sulphureted mercury can be readily resolved into free mercury, thereby permittingV the economic recovery of the metal from Vthe by-product.

lis

. In spite of these specially `attractive charagent, no practical process has been proposed, in so far asI amaware, for its use as such, because of the diliculty in cleansing the metal in a practical way so as to present the necessary fresh metallicsurfaces to the sulphur content of the oil.

I have discovered that `the application of c, mercury for desulphurizing purl voses can be made practical. by treating t e mercury chemically during the desulphurizingV process i to Wash out or remove the sulpliureted mercury fromthe mercury. I have also found` that the best results are secured by maintaining the body of mercury incontact with the chemical, which preferably is in the form of a `Water solution ofanalliali sulphide with or ywithout an alkali hydroxide superimposed on the body of mercury, the hydrocarbon oil being passed upwardly through the mercury and thewater solution so that the sulphureted mercury is washed out of the mercury and a fresh metallic surface is continually presented to the sulphur in t-he oil. The materials I have found `to give the best results'in the `,water solution are sodium or potassium sulphide or mixtures thereof with or Without the addition of sodium or potassium hydroxide or mixtures thereof, but I do not limit myself to the use of any particular compsition for thecleansing solution. Solutions of sodium orpotassium sulphide or mixtures thereof in water of various concentrations can be used for eil'ecting'the necessarycleansing of theimercur'y, but I Yhave found it. technically ladvantageous to use concentrated solutions particularly because ofthe increased solubility therein of sulphureted mercury. I have found it particularly advantageous to add sodium or potassium hydroxide or mixtures thereof to such concentrated solutions of sodium or potassium sulphide or mixtures thereof in water in order to increase their solvent action on sulphureted mercury.

lIn the application of my invention, Ido

not limit myself to any particular methodl for applying the cleansing solution. It can be `applied intermittentlyy or constantly, but I prefer to leep itconstantlyin contact with the metallic mercury during the desulphurizing of an oil in order to maintain a maxi-` mum total desulphurizing eiiectA for a iven amount of mercury under a given set o conditions. c' c In carrying out myinventlon Iarrange for replacement of the .cleansingl solution.4 acV-` cording as it becomes saturated with sulphureted mercury. I do Wnot limit myself to any particular .method for eii'ecting this replacement of cleansing solution since it can be done in any convenient manner. c

Furthermore, my invention is adaptable not only to the batch method of treating but also to the continuous method. The con-- tinuous method, I prefer, ,because of technical advantages involved;

. To illustrate my invention, I willdescribe the purification and desulphurization, in a continuous manner, of motor fuel distillate to which my invention is particularly adaptable but .not necessarily coniined. Before doing so,vI will describe the apparatus which I have successfully used, but'I make no claimto any apparatus sincemy invention may be applied inany apparatus of convenient construction.

a 5 foot lengthof 12 inch standard iron pipe,

having a bottom" distributing plate containing 34'holes, 6 each, fg of an inch in diameter, and a top plate 7 carrying afilling hole 8, 1

inch in diameter. Each of the individual reaction vvessels receives a charge of mercury `9, 12 inches indepth, upon which is superi imposed a charge of 15 gallons of cleansing solution 10. Thisparticular cleansinglsolution ,is approximately ,of the followingV composition z-sodiuin sul hide (NazS 3%, sodium hydroxide (NagH) 25% an water' las 72%. The three reaction bottles are connected in series, the oil entering each vessel through the bottom distributing plate.

The motor fuel distillate is forced continuously through the system by a pump 12 under substantially atmospheric temperature conditions, passing from the storage tank l through the three reaction vessels 2, 3 and 4, and then into the settling tank 5, Where any cleansing solution mechanically carried along by the distillate stream settles out, and finally issues therefrom as finished distillate. Replacement of the cleansing solution is made when it becomes spent with respect to solvent action on the sulphureted mercury.

The finished distillate so obtained is sweet or free from sour sulphur and non-corrosive or free from corrosive sulphur.

WhileI have described my process specilically With reference to motor fuel distillate with its natural sulphur content, sour and corrosivey or both, I wish it to be understood that it is likewise effective for such distillate and other distillates from which the sour sulphur has been Wholly or partially re` moved by any previous specific desulphurizing treatment, and is particularly effective for remoing free or elementary sulphur from any hydrocarbon oil.

What I claim as my invention and desire to secure by Letters Patent is: v

l. The process of desulphurizing hydrocarbon oils which consists in subjecting the oil to be treated to the action of metallic mercury and simultaneously subjecting the metallic mercury to a Water solution of an alkali sulphide.

j 2. The process of desulphurizing hydrocarbon oils which consists in subjecting the oil to be treated to the action of metallic mercury, and simultaneously subjecting the metallic mercury to a Water solution of an alkali sulphide and an alkali hydroxide.

3. The process of desulphurizing hydrocarbon oils which consists in passing the oil upwardly first through a body of metallic mercuryfand through a Solution of an alkali sulphide in contact with the body of metallic mercury. V

4. The process of desulphurizing hydrocarbon oils which consists in passing the oil upwardly first through a body of metallic mercury and through a solution of an alkali sulphide and an alkali hydroxide in contact With the body of metallic mercury.

5. The` process of desulphurizing hydrocarbon oils Which consists in simultaneously subjecting the oil at substantially atmospheric conditions to the action of metallic mercury and subjecting the mercury'to a Water solution of an alkali sulphide.

G. The process of desulphurizing hydrocarbon oils which Vconsists in simultaneously subjecting the oil at substantially atmospheric conditions to the action of metallicy mercury and subjecting the mercury to a Water solution of an alkali sulphide and an alkali hydroxide.

7. The process of desulphurizing hydrof carbon `oils which consists in passing the oil at substantially atmospheric conditions through a body of metallic mercury which is in contact With a Water solution of an alkali sulphide. 'l

8. The process of desulphurizing hydrocarbon oils which consists in passing the oil at substantially atmospheric conditions through a body of metallic mercury Which is in contact With a Water solution of an alkali sulphide and an alkali hydroxide.

ROBERT c." MoRAN. 

